Pressure-sensitive adhesive composition

ABSTRACT

The present invention relates to a pressure sensitive adhesive composition, a polarizer and a liquid crystal display device. The present invention may provide a pressure sensitive adhesive which can have excellent stress relaxation characteristic to effectively inhibit light leakage by dimension change of optical films such as polarizing plates. In addition, a pressure sensitive adhesive having excellent physical properties such as adhesion durability and workability may be provided.

This application is a continuation application of U.S. patentapplication Ser. No. 13/512,289 filed May 25, 2012, which is a NationalStage Entry of International Application No. PCT/KR2010/008447 filedNov. 26, 2010, and claims the benefit of Korean Application Nos.10-2009-0115697 filed on Nov. 27, 2009 and 10-2009-0115695 filed on Nov.27, 2009, which are hereby incorporated by reference for all purposes asif fully set forth herein.

TECHNICAL FIELD

The present invention relates to a pressure sensitive adhesivecomposition.

BACKGROUND ART

A polarizing plate is an optical member included in a liquid crystaldisplay (LCD). The polarizing plate may have a multilayer structure of apolarizing element comprising an iodine compound or a dichroicpolarizing material, which is arranged in a given direction, and aprotective film to protect the element and to be formed on one or bothsides thereof. In addition, the polarizing plate may further comprise anadditional functional film such as a retardation plate, a wide viewangle compensation plate or a brightness enhancing film.

Each film consisting of a multilayer polarizing plate is made ofmaterials having molecular structures and compositions different fromeach other. Therefore, each film in the polarizing plate representsphysical properties different from each other. Especially, there is aproblem that dimensional stability is lowered depending on difference ofshrinkage or expansion behavior by each material in the polarizing plateunder a severe condition such as high temperature or high humiditycondition.

For example, when the polarizing plate is fixed by a pressure sensitiveadhesive, stress is focused on the protective film, and the like, by theabove difference of behavior under the severe condition to causebirefringence and a light leakage phenomenon called as a light beamingphenomenon.

As a method for solving such problems, a technique to provide thepressure sensitive adhesive with stress relaxation characteristic hasbeen known. Specifically, a method of designing the pressure sensitiveadhesive to have high creep against an external stress and to be easilymodified has been known (ex. Korean Unexamined Patent Publication No.1998-079266, Japanese Unexamined Patent Publication No. 2002-047468).

However, in the above technique, the pressure sensitive adhesive hasvery low tailoring property and workability. If the tailoring propertyand workability are lowered as such, there are problems that onmass-producing optical films such as polarizing plates, defects, such asextrusion or pressing of the pressure sensitive adhesive, are caused, sothat yield decreases highly.

Furthermore, there is an attempt to minimize light leakage by designingthe pressure sensitive adhesive very hard.

For example, in Japanese Unexamined Patent Publication Nos. 2007-197659and 2007-212995, a technique of preparing a pressure sensitive adhesiveis disclosed, which is prepared by adding a multifunctional acrylate, anisocyanate hardener and a photoinitiator to an acrylic polymercontaining a carboxyl group, followed by UV irradiation. In JapaneseUnexamined Patent Publication No. 2007-212995, a technique of preparinga pressure sensitive adhesive is disclosed, which is prepared bycombining a copolymer containing a hydroxyl group and a copolymercontaining a carboxyl group in a given ratio, and adding amultifunctional acrylate, a multifunctional isocyanate hardener and aphotoinitiator thereto, followed by UV irradiation.

However, said pressure sensitive adhesives have very low initialadhesive strength depending on storage modulus (G′), so that durabilityunder high temperature or high humidity is lowered, or much lightleakage is caused.

DISCLOSURE Technical Problem

The present invention is intended to provide with a pressure sensitiveadhesive composition.

Technical Solution

The present invention relates to a pressure sensitive adhesivecomposition comprising a crosslinkable acrylic polymer having a weightaverage molecular weight of more than 500,000 and less than 1,000,000;and a multifunctional crosslinker, wherein an interpenetrating polymernetwork (hereinafter, sometimes called as “IPN”) structure is embodiedin a cured state.

In one aspect, the present pressure sensitive adhesive composition maybe used as a pressure sensitive adhesive composition for polarizingplates and specifically, for attaching the polarizing plate to a liquidcrystal panel.

The pressure sensitive adhesive composition of the present invention isexplained in detail below.

The present pressure sensitive adhesive composition comprises acrosslinkable acrylic polymer having a weight average molecular weightof 500,000 and 1,000,000. The weight average molecular weight hereinmeans a converted value to polystyrene as measured by a gel permeationchromatography (GPC). Also, the molecular weight means a weight averagemolecular weight unless it is mentioned specifically otherwise herein.

The term “crosslinkable acrylic polymer” herein means an acrylic polymercomprising a functional group which may be reacted with amultifunctional crosslinker. Also, the term “multifunctionalcrosslinker” means a compound having at least two functional groupswhich may be reacted with the crosslinkable functional group included insaid acrylic polymer to embody a crosslinked structure.

A molecular weight of the crosslinkable acrylic polymer herein exceeds500,000, whereby the cohesive attraction and durability thereof may beexcellently maintained, and the molecular weight is controlled to lessthan 1,000,000 for the pressure sensitive adhesive to representexcellent stress relaxation characteristic, so that the light leakagephenomenon may be effectively inhibited. The molecular weight of thecrosslinkable acrylic polymer herein may be preferably, 600,000 to900,000 and more preferably, 600,000 to 800,000.

As long as the crosslinkable acrylic polymer herein has theaforementioned range of the molecular weight and comprises acrosslinkable functional group, a specific composition thereof is notparticularly limited. In one aspect, said polymer may be a polymercomprising 80 to 99.8 parts by weight of (meth)acrylic acid estermonomer; and 0.02 to 20 parts by weight of a crosslinkable monomer as apolymerized unit. The term “part by weight” means a ratio by weight.

A specific kind of (meth)acrylic acid ester monomer herein is notparticularly limited, and for example, alkyl (meth)acrylate may be used.In view of controlling cohesive attraction, glass transition temperatureand adhesion of the pressure sensitive adhesive, alkyl (meth)acrylatehaving an alkyl group with 1 to 14 carbon atoms may be used, withoutlimiting thereto. An example of such a monomer may include methyl(meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl(meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate,sec-butyl (meth)acrylate, pentyl (meth)acrylate, 2-ethylhexyl(meth)acrylate, 2-ethylbutyl (meth)acrylate, n-octyl (meth)acrylate,isooctyl (meth)acrylate, isononyl (meth)acrylate, lauryl (meth)acrylateand tetradecyl (meth)acrylate, wherein one or two or more, incombination thereof, of the foregoing may be used. The present polymermay comprise (meth)acrylic acid ester monomer in an amount of 80 to 99.8parts by weight based on weight of the crosslinkable functional group,whereby the initial bond strength, cohesive attraction and durabilitymay be appropriately maintained.

The present polymer comprises a crosslinkable monomer in a polymerizedform. The crosslinkable monomer is a monomer which may provide theacrylic polymer with a crosslinkable functional group that can bereacted with the multifunctional crosslinker.

An example of the crosslinkable monomer may include a monomer having ahydroxyl group, a carboxyl group, a nitrogen containing group such as asubstituted or unsubstituted amide group, an isocyanate group or aglycidyl group, of which a monomer containing a hydroxyl group or acarboxyl group is preferably used, without limiting thereto. In a fieldof preparing pressure sensitive adhesives, various monomers, which canprovide the polymer with each of said functional groups, are known. Forexample, an example of said monomer containing a hydroxyl group mayinclude 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate,4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate,8-hydroxyoctyl (meth)acrylate, 2-hydroxyethyleneglycol(meth)acrylate or2-hydroxypropyleneglycol (meth)acrylate, and the like; an example of themonomer containing a carboxyl group includes (meth)acrylic acid,2-(meth)acryloyloxy acetic acid, 3-(meth)acrylolyloxy propanoic acid,4-(meth)acryloyloxy butanoic acid, acrylic acid dimer, itaconic acid,maleic acid and maleic anhydride, and the like. Here, one or two ormore, in combination thereof, of the foregoing may be used.

In the present crosslinkable polymer, the crosslinkable monomer may beincluded in an amount of 0.02 to 20 parts by weight based on weight of(meth)acrylic acid ester monomer. Therefore, endurance reliability,adhesion and/or peel force of the pressure sensitive adhesive may beeffectively maintained.

The crosslinkable acrylic polymer herein may further comprise a monomerrepresented by the following chemical formula 1 as a polymerized unit,if desired. The monomer of chemical formula 1 may be added for thepurpose of controlling glass transition temperature or providing otherfunctionality.

wherein, R₁ to R₃ represent each independently hydrogen or alkyl, R₄represents cyano; phenyl unsubstituted or substituted with alkyl;acetyloxy; or COR₅, where R₅ represents amino or glycidyloxyunsubstituted or substituted with alkyl or alkoxyalkyl.

In definitions of R₁ to R₅ of the above formula, alkyl or alkoxy meansalkyl or alkoxy having 1 to 8 carbon atoms, and is preferably methyl,ethyl, methoxy, ethoxy, propoxy or butoxy.

The specific example of said monomer of chemical formula 1 may includeone or two or more of a nitrogen containing monomer such as(meth)acrylonitrile, (meth)acrylamide, N-methyl (meth)acrylamide orN-butoxy methyl (meth)acrylamide; a styrene monomer such as styrene ormethyl styrene; glycidyl (meth)acrylate; or a carbonic acid vinyl estersuch as vinyl acetate, and the like, but is not limited thereto. Whenthe present polymer comprises said monomer of chemical formula 1, thecontent may be 20 parts by weight, based on weight of (meth)acrylic acidester monomer.

A method of preparing said crosslinkable acrylic polymer herein is notparticularly limited. For example, the polymer may be prepared byapplying a monomeric mixture comprising the desired monomers to apolymerization method such as solution polymerization, photopolymerization, bulk polymerization, suspension polymerization oremulsion polymerization. Preferably, the solution polymerization hereinis used, but is not limited thereto.

The present pressure sensitive adhesive composition comprises amultifunctional crosslinker that may be reacted with a crosslinkableacrylic polymer to embody a crosslinked structure.

The usable specific crosslinker herein is not particularly limited toany kind and may be appropriately selected from general crosslinkers,such as an isocyanate compound, an epoxy compound, an aziridine compoundand a metal chelate compound, considering a kind of the crosslinkablefunctional group to be included in the polymer. A specific example ofsaid isocyante compound may include tolylene diisocyante, xylenediisocyante, diphenylmethane diisocyante, hexamethylene diisocyante,isophorone diisocyante, tetramethylxylene diisocyante or naphthalenediisocyante, and the like, or a compound obtained by reacting a polyolcompound such as trimethylol propane with said isocyanate compound maybe used. A specific example of the epoxy compound may include one ormore selected from the group consisting of ethyleneglycol diglycidylether, triglycidyl ether, trimethylolpropane triglycidyl ether,N,N,N′,N′-tetraglycidyl ethylenediamine and glycerine diglycidyl ether;and a specific example of the aziridine compound may include one or moreselected from the group consisting ofN,N′-toluene-2,4-bis(1-aziridinecarboxamide),N,N′-diphenylmethane-4,4′-bis(1-aziridinecarboxamide), triethylenemelamine, bisisophthaloyl-1-(2-methylaziridine) andtri-1-aziridinylphosphine oxide, but is not limited thereto. Inaddition, a specific example of said metal chelate compound may includea compound that a multivalent metal such as aluminum, iron, zinc, tin,titanium, antimony, magnesium and/or vanadium is coordinated with acetylacetone or ethyl acetoacetate, and the like, but is not limited thereto.

In the composition of the present invention, said crosslinker may beincluded in an amount of 0.01 to 10 parts by weight, and preferably 0.01to 5 parts by weight, relative to 100 parts by weight of a crosslinkableacrylic polymer. The cohesive attraction of the pressure sensitiveadhesive may be maintained by containing the crosslinker in an amount ofat least 0.01 parts by weight, and the endurance reliability may beoutstandingly maintained by containing it in an amount of up to 10 partsby weight.

The present pressure sensitive adhesive composition may further comprisea non-crosslinkable acrylic polymer, specifically, a non-crosslinkableacrylic polymer having a molecular weight of more than 500,000 and lessthan 1,000,000. The term “non-crosslinkable acrylic polymer” means anacrylic polymer that contains no intermolecular functional group whichmay be reacted with a multifunctional crosslinker. The non-crosslinkablepolymer may act on regulating a gel fraction of a crosslinkable polymerto form a gel by the multifunctional crosslinker, plasticizing apressure sensitive adhesive by being penetrated into or connected to thecrosslinked network (IPN) of the pressure sensitive adhesive andincreasing elasticity and flexibility of the adhesive at the same time,and inhibiting a light leakage phenomenon.

Said non-crosslinkable acrylic polymer herein may have a molecularweight of more than 500,000 and less than 1,000,000, preferably 600,000to 900,000, and more preferably 600,000 to 800,000. By controlling themolecular weight of the non-crosslinkable acrylic polymer in the aboverange, the pressure sensitive adhesive may have excellent cohesiveattraction, endurance reliability and stress relaxation characteristicat the same time.

Furthermore, as long as the non-crosslinkable acrylic polymer herein hasthe aforementioned weight average molecular weight, its specificcomposition is not particularly limited.

For example, said non-crosslinkable acrylic polymer may be a polymerthat (meth)acrylic acid ester monomer is included as a polymerized unit.The usable (meth)acrylic acid ester monomer is not particularly limitedto any kind, and the same monomers as described in the aforementionedcrosslinkable acrylic polymer may be used. In addition, the monomericmixture forming said non-crosslinkable acrylic polymer may comprise anadditional monomeric component of said monomer of chemical formula 1, aslong as it contains no crosslinkable monomer.

When a non-crosslinkable polymer is included in the present pressuresensitive adhesive composition, a ratio of the non-crosslinkable acrylicpolymer to the crosslinkable acrylic polymer (non-crosslinkable acrylicpolymer/crosslinkable acrylic polymer) by weight may be, for example, 0to 1, preferably 0.0001 to 1, more preferably 0.01 to 0.5, and mostpreferably 0.1 to 0.4. By controlling the ratio as such, endurancereliability under a severe condition may be outstandingly maintained.

The present pressure sensitive adhesive composition may further comprisea multifunctional acrylate. Said multifunctional acrylate may bepolymerized on curing to embody a crosslinked structure.

The multifunctional acrylate is not particularly limited to any kind.For example, it may include a difunctional acrylate such as1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate,neopentylglycol di(meth)acrylate, polyethyleneglycoldi(meth)acrylate,neopentylglycol adipate di(meth)acrylate, hydroxypivalic acidneopentylglycol di(meth)acrylate, dicyclopentanyl di(meth)acrylate,caprolactone modified dicyclopentenyl di(meth)acrylate, ethyleneoxidemodified di(meth)acrylate, di(meth)acryloxy ethyl isocyanulate,allylated cyclohexyl di(meth)acrylate, tricyclodecanedimethanol(meth)acrylate, dimethylol dicyclopentane di(meth)acrylate,ethyleneoxide modified hexahydrophthalic acid di(meth)acrylate,tricycloecane dimethanol (meth)acrylate, neopentylglycol modifiedtrimethylpropane di(meth)acrylate, adamantane di(meth)acrylate or9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene; a trifunctional acrylatesuch as trimethylolpropane tri(meth)acrylate, dipentaerythritoltri(meth)acrylate, propionic acid modified dipentaerythritoltri(meth)acrylate, pentaerythritol tri(meth)acrylate, propyleneoxidemodified trimethylolpropane tri(meth)acrylate, 3-functional urethane(meth)acrylate or tris(meth)acryloxy ethylisocyanulate; atetrafunctional acrylate such as diglycerine tetra (meth)acrylate orpentaerythritol tetra(meth)acrylate; a pentafunctional acrylate such aspropionic acid modified dipentaerythritol penta(meth)acrylate; and ahexafunctional acrylate such as dipentaerythritol hexa(meth)acrylate,caprolactone modified dipentaerythritol hexa(meth)acrylate or urethane(meth)acrylate (ex. a reactant of an isocyanate monomer andtrimethylolpropane tri(meth)acrylate), but is not limited thereto.

Here, one or two or more of the above multifunctional acrylates may beused alone or in combination therewith. Especially, in view of realizingthe more outstanding durability, it is preferred to use at least3-functional acrylates having a molecular weight of less than 1,000, butis not limited thereto.

Especially, it is preferred to use an acrylate comprising a cyclicstructure in a molecular structure as a multifunctional acrylate. Here,the cyclic structure is any structure of a carbocyclic structure or aheterocyclic structure; or a monocyclic or polycyclic structure. Inparticular, an example of the cyclic structure included in saidmultifunctional acrylate may include a cycloalkyl cyclic structurehaving 3 to 12 carbon atoms, preferably 3 to 8 carbon atoms, such ascyclopentane, cyclohexane or cycloheptane, wherein at least 1,preferably 1 to 5, and more preferably 1 to 3 of said cyclic structuremay be included in the acrylate, and at least one heteroatom such as O,S or N may be also included therein.

A specific example of a multifunctional acrylate comprising a cyclicstructure as above to be capable of being used herein may include amonomer having an isocyanulate structure such as tris(meth)acryloxyethyl isocyanulate, an isocyanulate modified urethane acrylate (ex. areactant of an isocyanate compound having a cyclic structure in themolecule, for example, isophorone disocyante, and an acrylate compound,for example, trimethylolpropane tri(meth)acrylate or pentaerythritoltri(meth)acrylate, and the like), and the like, but is not limitedthereto.

In the present pressure sensitive adhesive composition, themultifunctional acrylate may be included in an amount of more than 5parts by weight and less than 15 parts by weight, relative to 100 partsby weight of the aforementioned crosslinkable acrylic polymer. Bycontrolling the ratio of the multifunctional acrylate by weight as such,the suitably crosslinked structure may be embodied and endurancereliability may be also excellently maintained.

The present pressure sensitive adhesive composition embodies the IPNstructure in a cured state. The term “a cured state of a pressuresensitive adhesive composition” means a state that the composition ischanged into a form of the pressure sensitive adhesive viaphoto-irradiation, heating and/or aging processes, and the like. Theterm “photo-irradiation” means electromagnetic wave irradiation that mayaffect a photocurable, photocrosslinkable or photopolymerizable compoundsuch as a multifunctional acrylate and cause a hardening, crosslinkingor polymerizing reaction. Electromagnetic waves include particle beamssuch as α-particle beams, proton beams, neutron beams and electron beamsas well as microwaves, infrared (IR), ultraviolet (UV), X-ray and γ-ray.

The term “IPN structure” means a state that at least two crosslinkedstructures are present in the pressure sensitive adhesive. In oneaspect, the IPN structure may also mean a structure comprising at leasttwo crosslinked structures present in a state that each other isintertwined, entangled or penetrated. For example, when the presentcomposition comprises the multifunctional acrylate, said IPN structuremay comprise a crosslinked structure by a reaction of said crosslinkableacrylic polymer and a multifunctional crosslinker, that is, acrosslinked structure by a crosslinkable acrylic polymer crosslinkedwith a multifunctional crosslinker (hereinafter, optionally referred toa first crosslinked structure) and a crosslinked structure by thepolymerized multifunctional acrylate (hereinafter, optionally referredto a second crosslinked structure), wherein such first and secondcrosslinked structures may be present in a state that each other ispenetrated or entangled. The pressure sensitive adhesive comprises theIPN structure, whereby acrylic polymers having low molecular weight areused but the pressure sensitive adhesive without the lowered endurancereliability and with excellent adhesion property, re-detachability andworkability, and the like may be embodied.

The present pressure sensitive adhesive composition may further comprisea photoinitiator. Said photoinitiator may carry out a polymerizationreaction of the multifunctional acrylate with photo irradiation toprovide inside of the pressure sensitive adhesive with a crosslinkedstructure.

The usable photoinitiator herein is not particularly limited to anykind, as long as it may generate a radical with photo irradiation toinitiate a polymerization reaction of a multifunctional acrylate. Aspecific example of the usable photoinitiator herein may includebenzoins, hydroxyl ketones, aminoketones or phosphine oxides, and thelike, and more particularly, benzoin, benzoin methyl ether, benzoinethyl ether, benzoin isopropyl ether, benzoin n-butyl ether, benzoinisobutyl ether, acetophenone, dimethylamino acetophenone,2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone,2-hydroxy-2-methyl-1-phenylpropan-1-one,1-hydroxycyclohexylphenylketone,2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propan-1-one,4-(2-hydroxyethoxy)phenyl-2-(hydroxy-2-propyl)ketone, benzophenone,p-phenylbenzophenone, 4,4′-diethylaminobenzophenone,dichlorobenzophenone, 2-methylanthraquinone, 2-ethylanthraquinone,2-t-butylanthraquinone, 2-aminoanthraquinone, 2-methylthioxanthone,2-ethylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone,2,4-diethylthioxanthone, benzyldimethylketal, acetophenonedimethylketal, p-dimethylamino benzoic acid ester,oligo[2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone] and2,4,6-trimethylbenzoyl-diphenyl-phosphineoxide, and the like, but is notlimited thereto. Here, one or two or more of the foregoing may be used.

The photoinitiator herein may be included in an amount of 0.01 to 10parts by weight, preferably 0.01 to 5 parts by weight, relative to 100parts by weight of a crosslinkable acrylic polymer, or of 0.2 to 20parts by weight, relative to 100 parts by weight of a multifunctionalacrylate. If the content of the photoinitiator is too low, it isapprehended that the polymerization or curing reaction will not besmoothly carried out. If the content is too high, it is apprehended thatphysical properties such as endurance reliability or transparency willbe lowered.

The present pressure sensitive adhesive composition may further comprisea silane coupling agent. Such a coupling agent may enhance adhesion andbond stability between a pressure sensitive adhesive and a glasssubstrate to improve heat resistance and humidity resistance. Inaddition, said coupling agent may act on improving bond reliability,when the pressure sensitive adhesive has been left in high temperatureor high humidity condition for a long time. An example of the usablecoupling agent herein may include γ-glycidoxypropyl triethoxy silane,γ-glycidoxypropyl trimethoxy silane, γ-glycidoxypropyl methyldiethoxysilane, γ-glycidoxypropyl triethoxy silane, 3-nercaptopropyl trimethoxysilane, vinyltrimethoxysilane, vinyltriethoxy silane,γ-methacryloxypropyl trimethoxy silane, γ-methacryloxy propyl triethoxysilane, γ-aminopropyl trimethoxy silane, γ-aminopropyl triethoxy silane,3-isocyanato propyl triethoxy silane, γ-acetoacetatepropyltrimethoxysilane, γ-acetoacetatepropyl triethoxy silane, β-cyanoacetyltrimethoxy silane, β-cyanoacetyl triethoxy silane,acetoxyacetotrimethoxy silane, and one or two or more, in combinationtherewith, of the foregoing may be used. Here, it is preferred to use asilane coupling agent having an acetoacetate group or a β-cyanoacetylgroup, but is not limited thereto. In the present composition, thesilane coupling agent may be included in an amount of 0.01 to 5 parts byweight, preferably 0.01 to 1 part by weight, relative to 100 parts byweight of an acrylic resin. If the content of the coupling agent is lessthan 0.01 parts by weight, it is apprehended that the increased effectof adhesion strength will be slight. If it is more than 5 parts byweight, endurance reliability will be lowered.

In view of controlling adhesion performance, the present pressuresensitive adhesive composition may further comprise a tackifier. Such atackifier is not particularly limited to any kind and, for example, oneor two or more of a hydrocarbon resin or hydrogenated products thereof,a rosin resin or hydrogenated products thereof, a rosin ester resin orhydrogenated products thereof, a terpene resin or hydrogenated productsthereof, a terpene phenol resin or hydrogenated products thereof, apolymerized rosin resin or a polymerized rosin ester resin may be usedalone or as a mixture. The tackifier may be included in an amount of 1to 100 parts by weight, relative to 100 parts by weight of acrosslinkable acrylic polymer. If said amount is less than 1 part byweight, it is apprehended that an effect of addition will be slight. Ifit is more than 100 parts by weight, the increased effect ofcompatibility and/or cohesive attraction will be lowered.

The present pressure sensitive adhesive composition may further compriseat least one additive selected from the group consisting of an epoxyresin, a crosslinker, a ultraviolet light stabilizer, an antioxidant, atoning agent, a reinforcing agent, a filler, a defoamer, a surfactantand a plasticizer in a range which does not affect the effect of theinvention.

By setting the polymer to have a low molecular weight, the presentinvention has a benefit that the coating process can be effectivelycarried out even in a state of setting the coating liquid to have highsolid content. Therefore, productivity of optical elements may bemaximized.

That is, the molecular weight of the polymer is related to variousphysical properties such as durability or coating property of thepressure sensitive adhesive. For example, when the polymer has too lowmolecular weight, cohesive attraction of the pressure sensitive adhesiveis lowered, whereby endurance reliability is lowered; for example,bubbles or a peel-off phenomenon occurs under high temperature or highhumidity condition. On the contrary, when the polymer has too highmolecular weight, durability of the pressure sensitive adhesive may beimproved. However, there is a problem that viscosity of the coatingliquid for preparing the pressure sensitive adhesive increases highly.Accordingly, in view of securing durability, the polymer is set in ahigh range to have a molecular weight of, usually, at least 1,200,000,generally, at least 1,500,000, but considering viscosity of the pressuresensitive adhesive composition (coating liquid), the solid content isset in a low range of about 12 to 15% by weight. In the existingprocess, the molecular weight of resin is set high to secure durabilityof the pressure sensitive adhesive. As a result, there are problems thatthe solid content of the coating liquid is necessarily lowered, theproduction efficiency is deteriorated, and it is difficult to uniformlycontrol thickness.

In the present invention, the coating process is capable of effectivelyproceeding even in a state of high solid content that the pressuresensitive adhesive composition has a solid content of at least 20% byweight, preferably at least 25% by weight. Said solid content means asolid content at a time when the present pressure sensitive adhesivecomposition is prepared in a form of a coating liquid, and the like andapplied to a process for preparing the pressure sensitive adhesive. Ifthe present pressure sensitive adhesive composition has a solid contentof less than 20% by weight, it is apprehended that effects for improvingproductivity and efficiency in the process for preparing the pressuresensitive adhesive or a polarizing plate will be lowered. In addition,the upper limit on said solid content herein is not particularly limitedand may be appropriately selected considering viscosity of thecomposition. For example, said solid content herein can be suitablycontrolled in a range of at least 50% by weight, preferably at least 40%by weight, and more preferably 30% by weight. Furthermore, the viscosityof the composition at room temperature may be in a range of 3,000 to12,000 cP, preferably 3,500 to 10,000 cP. Here, the room temperaturemeans usually a temperature of about 15 to 35° C. as a temperature in anatural state without heating or cooling.

The present invention relates to a polarizing plate comprising apolarizing element; and a pressure sensitive adhesive layer forattaching the polarizing plate to a liquid crystal panel, being formedon one or both sides of said polarizing element, and including apressure sensitive adhesive composition as mentioned above in a curedstate.

The polarizing plate to be used herein is not particularly limited toany kind and general species known in this field may be adapted. Forexample, said polarizing plate may comprise a polarizing element; and aprotective film formed on one or both sides of said polarizing element,wherein said pressure sensitive adhesive layer may be formed on one sideof said protective film.

The polarizing element included in the present polarizing plate is notparticularly limited to any kind, and for example, general species knownin this field such as a polyvinylalcohol polarizing element may beadapted without limitation.

The polarizing element is a functional film or sheet that may extractonly light vibrating in one direction from incident light vibrating inseveral directions. Such a polarizing element may be in a form thatdichroic colors are adsorbed and aligned to a polyvinylalcohol resinfilm. For example, a polyvinylacetate resin may gelate to obtain thepolyvinylalcohol resin constituting the polarizing element. The usablepolyvinylacetate resin may include a copolymer of vinyl acetate andother polymerizable monomers with vinyl acetate as well as a homopolymerof vinyl acetate. Here, an example of polymerizable monomers with vinylacetate one or two or more, in combination therewith, of unsaturatedcarbonic acids, olefins, vinylethers, unsaturated sulfonic acids andacrylamides with an ammonium group, but is not limited thereto. A degreeof gelation of the polyvinylalcohol resin may be usually 85 to 100 mol%, preferably at least 98 mol %. Said polyvinylalcohol resin may be alsoadditionally modified, and for example, polyvinylformal andpolyvinylacetal modified with aldehydes may be also used. In addition, apolymerization degree of the polyvinylalcohol resin may be usually 1,000to 10,000, preferably 1,500 to 5,000.

The polyinylalcohol resin as above may form a film to use as a disk filmof the polarizing element. A method of forming a film from thepolyvinylalcohol resin is not particularly limited and general methodsknown in this field may be used. A thickness of the disk film formed bythe polyvinylalcohol resin is not particularly limited, which may beappropriately controlled in a range of, for example, 1 to 150 μm. Saidthickness of the disk film may be controlled in at least 10 μmconsidering easiness of extension.

The polarizing element may be prepared via processes of stretching thepolyvinaylalcohol resin film as above (ex. uniaxially stretching),dyeing the polyvinylalcohol resin film with dichroic colors andadsorbing them thereto, treating the polyvinylalcohol resin film thatthe dichroic colors are adsorbed with boric acid aqueous solution andwashing it after treating with boric acid aqueous solution. As thedichroic colors, iodine or dichroic organic dyes, and the like may beused.

In addition, the present polarizing plate may further comprise aprotective film formed on one or both sides of said polarizing element.The protective film which can be included in the present polarizingplate is not particularly limited to any kind, and may be formed as amulti-layered film laminated with the protective film consisting of, forexample, cellulose films such as triacetyl cellulose; polyester filmssuch as polycarbonate films or polyethyleneterephthalate films;polyethersulfone films; and/or polyolefin films such as polyethylenefilms, polypropylene films, or polyolefin films having a cyclo ornorbornene structure or polyolefin films such as ethylene propylenecopolymer, and the like. Here, a thickness of said protective film isnot particularly limited and it may be formed to have a usual thickness.

A method of forming the pressure sensitive adhesive layer on thepolarizing plate is not particularly limited, and for example, a methodof applying the pressure sensitive adhesive composition (coating liquid)by a usual means such as the above bar coater and curing it, or a methodof first applying the pressure sensitive adhesive composition to asurface of a releasable substrate and curing it, and then transferringthe formed pressure sensitive adhesive layer to the polarizing plate,and the like, may be used.

It is preferred that the process for forming the pressure sensitiveadhesive layer is carried out after sufficiently removing bubble causingcomponents such as volatile components or reacting residues inside ofthe pressure sensitive adhesive composition (coating liquid). Therefore,problems, such as a pressure sensitive adhesive has so low cros slinkdensity or molecular weight that modulus of elasticity is lowered, andbubbles present between a glass plate and a pressure sensitive adhesivelayer at the elevated temperature have so large size that scatteringbodies are formed inside, can be inhibited.

In addition, a method of curing the present pressure sensitive adhesivecomposition on preparing the polarizing plate is not particularlylimited, and, for example, suitable electromagnetic wave irradiation forinducing polymerization, crosslinkage or curing reactions ofphotopolymerizable, photocros slinking or photocurable components in thecomposition, such as ultraviolet irradiation in combination withsuitable heating or even aging processes to be capable of inducing areaction of a crosslinkable polymer and a multifunctional crosslinker,may be carried out.

In case of applying the ultraviolet irradiation method herein, saidultraviolet irradiation may be carried out using means such as a highpressure mercury lamp, an electrodeless lamp or a xenon lamp. Also, inthe ultraviolet curing method, the irradiance level is not particularlylimited, as long as it is controlled to a degree that sufficient curingis obtained without damaging all physical properties. For example,preferably, illuminance is 50 to 1,000 mW/cm2 and light quantity is 50to 1,000 mJ/cm2.

The pressure sensitive adhesive layer prepared via the above procedureshas a gel content, as represented by the following general formula 2, ofpreferably at least 80% by weight and more preferably at least 90% byweight.

Gel content (% by weight)=B/A×100  [General Formula 2]

wherein, A represents a mass of said pressure sensitive adhesive, Brepresents a dry mass of insoluble fractions in said pressure sensitiveadhesive after depositing it in ethyl acetate at room temperature for 48hours.

If said gel content is less than 80% by weight, it is apprehended thatendurance reliability of the pressure sensitive adhesive under hightemperature and/or high humidity condition will be lowered.

The upper limit of said gel content herein is not particularly limited,and may be appropriately controlled, for example, in a range of up to99% considering stress relaxation characteristic of the pressuresensitive adhesive, and the like.

The present polarizing plate may further comprise at least onefunctional layer selected from the group consisting of a protectivelayer, a reflective layer, an antiglare layer, a retardation plate, awide view angle compensation film and a brightness enhancing film.

The present invention also relates to a liquid crystal display devicecomprising a liquid crystal panel that the polarizing plate according tothe present invention as mentioned above is attached to one or bothsides.

Said liquid crystal panel included in the liquid crystal display deviceof the present invention is not particularly limited to any kind.Various passive matrix types including TN (Twisted Nematic) type, STN(Super Twisted Nematic) type, F (ferroelectric) type and PD (polymerdispersed LCD) type, and the like; various active matrix types includingtwo terminal type and three terminal type; the known liquid crystalpanels including In-plane switching (IPS) mode panels and verticalalignment (VA) mode panels may be applied without limiting to any kind.In addition, other components included in the liquid crystal display ofthe present invention are not particularly limited to any kind, themethod of preparing the same are also not particularly limited. Generalcomponents in this field may be selected and used without limitation.

Advantageous Effects

In the present invention, the weight average molecular weight of thecrosslinkable acrylic polymer, which is reacted with a multifunctionalcrosslinker to embody a crosslinked structure, is set low to provide thepressure sensitive adhesive with excellent stress relaxationcharacteristic, whereby light leakage in accordance with the dimensionalchange of a polarizing plate may be effectively inhibited. Also, thepressure sensitive adhesive, which inhibits lowering of durabilityaccording to the low weight average molecular weight of the acrylicpolymer and has excellent physical properties such as adhesionproperties, re-detachability and workability, may be provided byembodying an interpenetrating polymer network therein.

DETAILED DESCRIPTION FOR CARRYING OUT THE INVENTION

The present invention is explained in more detail through examplesaccording to the present invention and comparative examples notaccording to the present invention below, but the scope of the presentinvention is not restricted by the following examples.

Preparation Example 1 Preparation of Crosslinkable Acrylic Polymer (A)

In a 1 L reactor with nitrogen gas refluxed and installing arefrigerator to easily regulate a temperature, 98 parts by weight ofn-butyl acrylate (n-BA) and 2 parts by weight of hydroxyethylmethacrylae (HEMA) were poured. Subsequently, 120 parts by weight ofethyl acetate (EAc) as a solvent was introduced thereto and nitrogen gaswas purged for 60 minutes to remove oxygen. Then, 0.03 parts by weightof azobisisobutyronitrile (AIBN) was introduced thereto with maintainingthe reactor at 60° C. and reacted for 8 hours to prepare a crosslinkableacrylic polymer (A) having a weight average molecular weight of about700,000. The weight average molecular weight herein was measured bygeneral gel permeation chromatography (GPC) method.

Preparation Examples 2 to 8 Preparation of Crosslinkable andNon-Crosslinkable Acrylic Polymers

Crosslinkable and non-crosslinkable acrylic polymers were prepared by amethod based on Preparation Example 1, except for monomer compositionand weight average molecular weights of the prepared polymers to beregulated as the following tables 1 and 2.

TABLE 1 Copoly- Copoly- Copoly- Copoly- mer (A) mer (B) mer (C) mer (D)Monomer n-BA/HEMA n-BA n-BA/AA n-BA/HEMA Composition (98/2) (100) (97/3)(99/1) (part by weight) M_(w) (10,000) 70 70 70 150 n-BA: n-butylacrylate HEMA: 2-hydroxyethyl methacrylate AA: acrylic acid M_(w):weight average molecular weight

TABLE 2 Copoly- Copoly- Copoly- Copoly- mer (A) mer (B) mer (C) mer (D)Monomer n-BA n-BA/HEMA n-BA n-BA/HEMA Composition (100) (99/1) (100)(98/2) (part by weight) M_(w) (10,000) 150 120 120 40 n-BA: n-butylacrylate HEMA: 2-hydroxyethyl methacrylate AA: acrylic acid M_(w):weight average molecular weight

Example 1 Preparation of Pressure Sensitive Adhesive Composition

12 parts by weight of tris(acryloxyethyl)isocyanulate (molecular weight:423, trifunctional, aronix M-315), 1.59 parts by weight of1-hydroxycyclohexyl phenyl ketone (Irg 184, manufactured by Ciba) as aphotoinitiator and 0.01 parts by weight of trimethylol modified tolylenediisocyanate (coronate L) as a crosslinker were formulated, relative to100 parts by weight of the crosslinkable acrylic polymer (A), to preparea pressure sensitive adhesive composition.

Preparation of Pressure Sensitive Adhesive Polarizer

The above prepared pressure sensitive adhesive composition was coated ona PET film (manufactured by Mitsubishi, MRF-38) having a thickness of 38μm and treated with a release sheet to have a thickness of 25 μm afterdrying, and dried in an oven at 110° C. for 3 minutes. Subsequently, thedried coating layer was stored in a constant temperature and humidityroom (23° C., 55% RH) for about 24 hours, and then laminated on a wideview (WV) liquid crystal layer of the polarizing plate coated on oneside therewith. Then, the laminated plate was subjected to ultravioletirradiation under the following condition to prepare a pressuresensitive adhesive polarizing plate.

<Condition for Irradiating Ultraviolet>

Ultraviolet irradiator: high pressure mercury lamp

Irradiation condition: Illuminance=600 mW/cm², Light quantity=150 mJ/cm²

Examples 2 to 4 and Comparative Examples 1 to 6

The pressure sensitive adhesive polarizing plates were prepared by themethod based on Example 1, except for composition of the pressuresensitive adhesive compositions to be changed as represented in thefollowing tables 3 and 4.

TABLE 3 Examples 1 2 3 4 Crosslinkable Kind A A C C copolymer Part byweight 100 100 100 100 Non- Kind — B — B crosslinkable Part by weight —25 — 25 polymer Crosslinkable: Non-crosslinkable 0 0.25 0 0.25 MFA KindM315 M315 M315 M315 Part by 12 12 12 12 weight Photoinitiator KindIrg184 Irg184 Irg184 Irg184 Part by 1.59 1.59 1.59 1.59 weightCrosslinker Kind Coro- Coro- Coro- Coro- nate L nate L nateL nate L Partby 0.01 0.07 0.04 0.07 weight M315: tris(acryloxyethyl)isocyanulate (Mw:423, 3-functional Irg184: 1-hydroxycyclohexyl phenyl ketone (Irg184,Ciba) Crosslinker: trimethylol modified tolylene diisocyanate (coronateL) Crosslinkable: Non-crosslinkable = Part by weight ofNon-crosslinkable acrylic copolymer/Part by weight of Crosslinkableacrylic polymer

TABLE 4 Comparative Examples 1 2 3 4 5 6 Crosslinkable Kind D D F F A Hcopolymer Part by 100 100 100 100 100 100 weight Non- Kind E — G — — —crosslinkable Part by 400 — 400 — — — polymer weight Crosslinkable: Non-4 0 4 0 0 0 crosslinkable MFA Kind M315 — M315 — — M315 Part by 12 — 12— — 12 weight Photoinitiator Kind Irg184 — Irg184 — — Irg184 Part by1.59 — 1.59 — — 1.59 weight Crosslinker Kind Coronate L Coronate LCoronate L Coronate L Coronate L Coronate L Part by 0.04 — 0.04 0.040.04 0.06 weight M315: tris(acryloxyethyl)isocyanulate (Mw: 423,3-functional Irg184: 1-hydroxycyclohexyl phenyl ketone (Irg184, Ciba)Crosslinker: trimethylol modified tolylene diisocyanate (coronate L)Crosslinkable: Non-crosslinkable = Part by weight of Non-crosslinkableacrylic copolymer/Part by weight of Crosslinkable acrylic polymer

For the pressure sensitive adhesive polarizing plates prepared inExamples and Comparative Examples, physical properties were measured bythe following methods and their results were summarized in Tables 5 and6 below.

1. Evaluation of Curl Property in Liquid Crystal Panel

The pressure sensitive adhesive polarizing plates prepared in Examplesand Comparative Examples were each attached to both sides of generalliquid crystal panels as top and bottom polarizing plates. Then, theliquid crystal panels, to which the polarizing plates were attached,were left in an oven at 80° C. for 72 hours, and removed from the ovento measure a degree of curling along four edges of the liquid crystalpanels within 5 minutes and to evaluate curl property depending on thefollowing standard.

<Evaluation Standard>

⊙: no occurrence of curl in liquid crystal panel

◯: slight occurrence of curl in liquid crystal panel

Δ: some occurrence of curl in liquid crystal panel

x: frequent occurrence of curl in liquid crystal panel

2. Evaluation of Endurance Reliability

The pressure sensitive adhesive polarizing plates prepared in Examplesand Comparative Examples were tailored in a size of 90 mm×170 mm toprepare specimens, which were then attached to both sides of glasssubstrates (110 mm×190 mm×0.7 mm) in a state of crossed opticalabsorption axes to prepare samples. Here, the applied presser was about5 Kg/cm², and the above procedures were carried out in a clean room tocause no bubbles or foreign materials. To identify humidity and heatresistance of the prepared samples, the samples were left at atemperature of 60° C. and under a 90% relative humidity condition for1,000 hours and observed of whether bubbles or peel-off were present. Inaddition, for heat resistance, the samples were left at a temperature of80° C. for 1,000 hours and then observed of whether bubbles or peel-offwere present. The state of specimens was evaluated after being left atroom temperature for 24 hours shortly before evaluation. Evaluationstandards for reliability are as follows.

<Evaluation Standard>

◯: no occurrence of bubbles or peel-off phenomenon

Δ: slight occurrence of bubbles or peel-off phenomenon

x: frequent occurrence of bubbles or peel-off phenomenon

3. Evaluation of Light Transmission Uniformity (Light Leakage)

Light transmission uniformity was measured using the same specimens asthose for evaluating endurance reliability. The above specimens wereirradiated with backlight and observed of whether a portion of lightleakage in a dark room was present. Specifically, the light transmissionuniformity was evaluated by a method of attaching pressure sensitiveadhesive polarizing plates (200 mm×200 mm) to both sides of glasssubstrates (210 mm×210 mm×0.7 mm) in a state crossed at 90 degrees andobserving them. Evaluation standards for light transmission uniformityare as follows.

<Evaluation Standard>

◯: it is difficult to identify a non-uniformity phenomenon in lighttransmission by the naked eye

Δ: slight presence of a non-uniformity phenomenon in light transmission

x: large presence of a non-uniformity phenomenon in light transmission

Each physical property measured in the above was summarized in thefollowing tables 5 and 6.

TABLE 5 Examples 1 2 3 4 Re-detachability ◯ ⊙ ◯ ⊙ Endurance Heatresistant ◯ ◯ ◯ ◯ Reliability condition Humidity and heat ◯ ◯ ◯ ◯resistant condition Light transmission uniformity ◯ ◯ ◯ ◯

TABLE 6 Comparative Examples 1 2 3 4 5 6 Re-detachability X Δ X Δ ⊙ ⊙Endurance Heat resistant ◯ ◯ ◯ Δ X X Reliability condition Humidity andheat ◯ ◯ ◯ Δ X X resistant condition Light transmission uniformity X Δ ◯Δ X X

As could be known from results of the above tables 5 and 6, in cases ofExamples 1 to 4 according to the present invention, re-detachability,endurance reliability and light transmission uniformity of the pressuresensitive adhesives were maintained all outstandingly. However, in casesof Comparative Examples 1 and 3 using polymers having a molecular weightof 1,000,000 or more, it was identified to highly reducere-detachability and light transmission uniformity, although the IPNstructures were embodied in the pressure sensitive adhesives.Furthermore, in case of Comparative Example 6 using a polymer having amolecular weight of 500,000 or less, stress relaxation characteristicwas secured to a certain degree, but durability was highly lowered.

Also, in cases of Comparative Examples 2 and 4 using polymers having amolecular weight of 1,000,000 or more and embodying no IPN structure inthe pressure sensitive adhesives, it could be identified that at leastone physical property of re-detachability, durability and controlcapability of light leakage control capability was lowered and itsbalance was poor. In addition, in case of Comparative Example 5embodying no IPN structure in the pressure sensitive adhesive, it wasalso identified that durability of the pressure sensitive adhesive washighly lowered.

What is claimed:
 1. A polarizing plate comprising a polarizing element;and a pressure sensitive adhesive layer for attaching the polarizingplate to a liquid crystal panel, being formed on one or both sides ofsaid polarizing element, and including a pressure sensitive adhesivecomposition in a cured state, wherein the pressure sensitive adhesivecomposition comprises a crosslinkable acrylic polymer having a weightaverage molecular weight of more than 500,000 and less than 1,000,000;and a multifunctional crosslinker, wherein an interpenetrating polymernetwork structure is embodied in a cured state.
 2. The polarizing plateaccording to claim 1, wherein the crosslinkable acrylic polymercomprises 80 to 99.8 parts by weight of a (meth)acrylic acid estermonomer; and 0.01 to 10 parts by weight of a crosslinkable monomer as apolymerized unit.
 3. The polarizing plate according to claim 1, whereinthe multifunctional crosslinker is one or more selected from a groupconsisting of an isocyanate compound, an epoxy compound, an aziridinecompound and a metal chelate compound.
 4. The polarizing plate accordingto claim 1, wherein the multifunctional crosslinker is included in anamount of 0.01 to 10 parts by weight relative to 100 parts by weight ofthe crosslinkable acrylic polymer.
 5. The polarizing plate according toclaim 1, the pressure sensitive adhesive composition further comprises anon-crosslinkable acrylic polymer having a weight average molecularweight of more than 500,000 and less than 1,000,000.
 6. The polarizingplate according to claim 5, wherein a ratio of the non-crosslinkableacrylic polymer to the crosslinkable acrylic polymer by weight is 0.0001to 0.1.
 7. The polarizing plate according to claim 1, the pressuresensitive adhesive composition further comprises a multifunctionalacrylate.
 8. The polarizing plate composition according to claim 7,wherein the multifunctional acrylate comprises a ring structure in themolecular structure thereof.
 9. The polarizing plate according to claim7, wherein the multifunctional acrylate is included in an amount of morethan 5 parts by weight and less than 15 parts by weight, relative to 100parts by weight of the crosslinkable acrylic polymer.
 10. The polarizingplate according to claim 7, wherein the interpenetrating polymer networkstructure comprises a cross-linked structure by an acrylic polymercross-linked with a multifunctional crosslinker and a cross-linkedstructure by a polymerized multifunctional acrylate.
 11. The polarizingplate according to claim 1, the pressure sensitive adhesive compositionfurther comprises a photoinitiator.
 12. The polarizing plate accordingto claim 1, the pressure sensitive adhesive composition furthercomprises a silane coupling agent or a tackifier.
 13. The polarizingplate according to claim 1, the pressure sensitive adhesive compositionhas a viscosity of 3,000 cP to 12,000 cP at room temperature and a solidcontent of at least 20% by weight.
 14. A liquid crystal display devicecomprising a liquid crystal panel that the polarizing plate according toclaim 1 is attached to one or both sides.